Catalyst compounds for olefin polymerization

ABSTRACT

Compounds useful as catalyst components for olefin polymerization. The compounds comprise derivatives of cyclopentadienyl complexes of the ZR or HF.

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

This is a divisional application of U.S. application Ser. No. 07/752,415filed Aug. 30, 1991, now U.S. Pat. No. 5,324,800, which is acontinuation of U.S. patent application Ser. No. 455,484 filed Dec. 22,1989 (now abandoned) which in turn was a continuation of U.S. patentapplication Ser. No. 728,111 filed Apr. 29, 1985 (now abandoned) whichin turn was a continuation of U.S. patent application Ser. No. 501,688filed Jun. 6, 1983 (now abandoned).

This invention relates to an improved process for polymerizing olefinsand more particularly to a method of controlling the molecular weightand/or the density of polyolefins produced so as to obtain polymerproduct in any desired range of molecular weight and densities. Theinvention particularly relates to the polymerization of the ethylene inthe presence or absence of comonomers to polyethylenes of controlledmolecular weight and density. The invention further relates to catalystcomponents and catalyst systems which are employed for the production ofpolyolefins of controlled molecular weight.

DESCRIPTION OF THE PRIOR ART

In U.S. Pat. No. 3,051,690 of Vandenberg, issued Aug. 28, 1962, there isdescribed a process of polymerizing olefins to high molecular weightpolyolefins of controlled molecular weight, as indicated by polymerviscosity, by the addition of controlled amounts of hydrogen to thepolymerization system. The molecular weight control was described asuseful in combination with a hydrocarbon insoluble catalyst systemcomprising the reaction product of a compound of a metal of Group IVB,VB, VIB and VIII with an organometallic compound of an alkali metal,alkaline earth metal, zinc, earth metal or rare earth metal. The patentteaches that increased use of hydrogen during the polymerization processresults in the decrease of polymer product viscosity.

It is further known that certain metallocenes such as bis(cyclopentadienyl) titanium or zirconium dialkyls in combination withaluminum alkyl/water cocatalyst form homogeneous catalyst systems forthe polymerization of ethylene.

German Patent Application 2,608,863 discloses the use of a catalystsystem for the polymerization of ethylene consisting of bis(cyclopentadienyl) titanium dialkyl, aluminum trialkyl and water.

German Patent Application 2,608,933 discloses an ethylene polymerizationcatalyst system consisting of zirconium metallocenes of the generalformula (cyclopentadienyl)_(n) ZrY_(4-n), wherein n stands for a numberin the range of 1 to 4, Y for R, CH₂ AlR₂, CH₂ CH₂ AlR₂ and CH₂CH(AlR₂)₂, wherein R stands for alkyl or metallo alkyl, an alumiunumtrialkyl cocatalyst and water.

European Patent Appln. No. 0035242 discloses a process for preparingethylene and atactic propylene polymers in the presence of ahalogen-free Ziegler catalyst system of (1) (cyclopentadienyl)_(n)MeY_(4-n) which n is an interger from 1 cyclopentadienyl compound of theformula to 4, Me is a transition metal, especially zirconium, and Y iseither hydrogren, a C₁ -C₅ alkyl or metallo alkyl group or a radicalhaving the following general formula CH₂ AlR₂, CH₂ CH₂ AlR₂ and CH₂CH(AlR₂)₂ in which R represents a C₁ -C₅ alkyl or metallo alkyl group,and (2) an alumoxane.

The above patents disclose that the polymerization process employing thehomogeneous catalyst system is also hydrogen sensitive for molecularweight control.

An advantage of the cyclopentadienyl-metal alumoxane catalyst system, istheir extremely high activity for ethylene polymerization. Anothersignificant advantage is that unlike olefin polymers produced in thepresence of conventional heterogeneous Ziegler catalyst, terminalunsaturation is present in polymers produced in the presence of thesehomogeneous catalysts. The use of hydrogen for molecular weight controlfor these homogeneous catalysts would be disadvantageous since theterminal unsaturation would become saturated and hence, the loss ofavailable sites for building functionalities into the olefin polymers.

I. EP 352452, the patentee discloses that relatively low molecularweight polymer products are obtained at higher polymerizationtemperatures and relatively high molecular weight polymers at lowpolymerization temperatures.

As in generally known in the art, it is desirable to maximizepolymerization temperatures in order to achieve high polymerizationactivity and reduce operating costs in terms of energy recovery. Thecatalyst disclosed in EP 35242 has certain disadvantages for theproduction of high molecular weight, high density resins since toproduce such polymer products, one must operate at low temperaturethereby increasing operating costs and decreasing catalytic activity.

It would be highly desirable to provide homogeneous catalysts which canbe usefully employed to produce high molecular weight polymer productsat conventional polymerization temperatures and to be able to controlmolecular weight and density of the polymer product without resorting totemperature control or hydrogen.

SUMMARY OF THE INVENTION

Accordingly, the present invention provides newcyclopentadienyl-metal/alumoxane catalysts for olefin polymerizationwhich catalyst can be usefully employed at high temperatures to obtainolefin polymer products having excellent properties with respect tomolecular weight, density and terminal unsaturation.

It has been discovered that the molecular weight of polymer product canbe controlled by the judicious selection of substituent on thecyclopentadienyl ring and use of ligands for the metallocenes. It hasfurther been discovered that comonomer content can be controlled by thejudicious selection of metallocenes. Hence, by the selection of catalystcomponents one can tailor polymer product with respect to molecularweight and density.

The catalysts usefully employed for the polymerization of ethylene andalpha-olefins to polyethylene homopolyolefins andcopolyethylene-alpha-olefin comprise new metallocenes in combinationwith alumoxanes. The metallocenes employed in accordance with thisinvention are organometallic coordination compounds which arecyclopentadienyl derivatives of a Group 4b, 5b and 6b metal of thePeriodic Table and include mono, di and tricyclopentadienyl and theirderivatives of the transition metals. The metallocenes include thoserepresented by the general formula (C₅ R'_(m))_(p) R"_(s) (C₅R'_(m))MeQ_(3-p) or R"_(s) (C₅ R'_(m))MeQ' wherein Me is a Group 4b, 5b,or 6b metal of the Periodic Table (Chemical rubber Company's Handbook ofChemistry & Physics, 48th edition). (C₅ R'_(m)) is a cyclopentadienyl orsubstituted cyclopentadienyl, each R', which can be the same ordifferent, is hydrogen or a hydrocarbyl radical such as alkyl, alkenyl,aryl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atomsor two carbon atoms are joined together to form a C₄ -C₆ ring, R" is aC₁ -C₄ alkylene radical, a dialkyl germanium or silicone, or a alkylphosphine or amine radical bridging two (C₅ R'_(m)) rings, Q is ahydrocarbon radical such as aryl, alkyl, alkenyl, alkylaryl, orarylalkyl radical having from 1 to 20 carbon atoms or halogen and can bethe same or different, Q' is an alkylidene radical having from 1 toabout 20 carbon atoms, s is 0 or 1, p is 0, 1 or 2; when p is 0, s is 0,m is 4 when s is 1 and m is 5 when s is 0 and at least one R' is ahydrocarbyl radical when Q is an alkyl radical.

The molecular weight of the polymer product can be further controlled bythe ratio of alumoxane to metallocene.

The present invention also provides a process for producingpolyethylenes having a high molecular weight at relatively hightemperatures. The process comprises polymerizing ethylene alone or inthe presence of minor amounts of higher alpha-olefins or diolefins inthe presence of the catalyst system described above.

The advantages of this invention are obtained by the use of derivativesof the cyclopentadienyl ring and/or other ligands for the metallocenesin order to control and tailor polymer molecular weight and/or comonomercontent.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed towards catalyst systems and acatalytic process for the polymerization of olefins, and particularlyethylene to high molecular weight polyethylenes such as linear lowdensity polyethylene (LLDPE) and high density polyethylene (HPDE). Thepolymers are intended for fabrication into articles by extrusion,injection molding, thermoforming, rotational molding, and the like. Inparticular, the polymers of this invention are homopolymers of ethylene,and copolymers of ethylene with higher alpha-olefins having from 3 toabout 10 carbon atoms and preferably 4 to 8 carbon atoms. Illustrativeof the higher alpha-olefins are butene-1, hexene-1 and octene-1.

In the process of the present invention, ethylene, either alone ortogether with alpha-olefins having 3 or more carbon atoms, ispolymerized in the presence of a catalyst system comprising at least onemetallocene and an alumoxane.

In accordance with this invention, one can also produce olefincopolymers particularly copolymers of ethylene and higher alpha-olefinshaving from 3-18 carbon atoms. As indicated above, the comonomer contentcan be controlled through the selection of metallocene catalystcomponent.

The alumoxanes are polymeric aluminum compounds which can be representedby the general formulae (R--Al--O)_(n) which is a cyclic compound andR(R--Al--O--)_(n) AlR₂, which is a linear compound. In the generalformula R is a C₁ -C₅ alkyl group such as, for example, methyl, ethyl,propyl, butyl and pentyl and n is an interger from 1 to about 20. Mostpreferably, R is methyl and n is about 4. Generally, in the preparationof alumoxanes from, for example, aluminum trimethyl and water, a mixtureof the linear and cyclic compounds is obtained.

The alumoxane can be prepared in various ways. Preferably, they areprepared by contacting water with a solution of aluminum trialkyl, suchas, for example, aluminum trimethyl, in a suitable organic solvent suchas benzene or an aliphatic hydrocarbon. For example, the aluminum alkylis treated with water in the form of a moist solvent. In an alternativemethod, the aluminum alkyl such as aluminum trimethyl can be desirablycontacted with a hydrated salt such as hydrated copper sulfate.

Preferably, the alumoxane is prepared in the presence of a hydratedcopper sulfate. The method comprises treating a dilute solution ofaluminum trimethyl in, for example, toluene, with copper sulfaterepresented by the general formula CuSO₄.5H₂ O. The ratio of coppersulfate to aluminum trimethyl is desirably about 1 mole of coppersulfate for 4 to 5 moles of aluminum trimethyl. The reaction isevidenced by the evolution of methane.

The new metallocene compounds usefully employed in accordance with thisinvention are the mono, bi and tricyclopentadienyl or substitutedcyclopentadienyl metal compounds. The metallocenes are represented bythe general formula

    (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MeQ.sub.3-p

and

    R".sub.s (C.sub.5 R'.sub.m).sub.2 MeQ'

wherein (C₅ R'_(m)) is a cyclopentadienyl or substitutedcyclopentsdienyl, each R' is the same or different and is hydrogen or ahydrocarbyl radical such as alkyl, alkenyl, aryl, alkylaryl, orarylalkyl radicals containing from 1 to 20 carbon atoms or two carbonatoms are joined together to form a C₄ -C₆ ring, R" is a C₁ -C₄ alkyleneradical, a dialkyl germanium or silicone, or a alkyl phosphine or amineradical bridging two (C₅ R'_(m)) rings, Q is a hydrocarbyl radical suchas aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radical having from1-20 carbon atoms or halogen and can be the same or different, Q' is analkylidene radical having from 1 to about 20 carbon atoms, s is 0 or 1,p is 0, 1 or 2; when p is 0, s is 0; m is 4 when s is 1 and m is 5 whens is 0, at least one R' is a hydrocarbyl radical when Q is an alkylradical and Me is a Group 4b, 5b, or 6b metal.

Exemplary hydrocarbyl radicals are methyl, ethyl, propyl, butyl, amyl,isoamyl, hexo, isobutyl, heptyl, octyl, nonyl, dicyl, cetyl,2-ethylhexyl, phenyl, and the like.

Exemplary alkylene radicals are methylene, ethylene, propylene, and thelike.

Exemplary halogen atoms include chlorine, bromine and iodine and ofthese halogen atoms, chlorine is preferred.

Exemplary of the alkylidene radical is methylidene, ethylidene andpropylidene.

Of the metallocenes, zirconocenes and titanocenes are most preferred.Illustrative but non-limiting examples of these metallocenes which canbe usefully employed in accordance with this invention aremonocyclopentadienyls titanocenes such as, cyclopentadienyl titaniumtrichloride, pentamethylcyclopentadienyl titanium trichloride;bis(cyclopentadienyl) titanium diphenyl, the carbene represented by theformula Cp₂ Ti═CH₂ .sup.. Al(CH₃)₂ Cl and derivatives of this reagentsuch as ##STR1## wherein Cp is a cyclopentadienyl or substitutedcylopentadienyl radical, and R'" is an alkyl, aryl or alkylaryl radicalhaving from 1-18 carbon atoms; substituted bis(Cp)Ti(IV) compounds suchas bis(indenyl)Ti diphenyl or dichloride, bis(methylcyclopentadienyl)Tidiphenyl or dihalides and other dihalide complexes; dialkyl, trialkyl,tetra-alkyl and penta-alkyl cyclopentadienyl titanium compounds such asbis(1,2-dimethylcyclopentadienyl)Ti diphenyl or dichloride,bis(1,2-diethylcyclopentadienyl)Ti diphenyl or dichloride and otherdihalide complexes; silicone, phosphine, amine or carbon bridgedcyclopentadiene complexes, such as dimethyl silyldicyclopentadienyltitanium diphenyl or dichloride, methyl phosphine dicyclopentadienyltitanium diphenyl or dichloride, methylenedicyclopentadienyl titaniumdiphenyl or dichloride and other dihalide complexes and the like.

Illustrative but non-limiting examples of the zirconocenes which can beusefully employed in accordance with this invention are,cyclopentadienyl zirconium trichloride, pentamethylcyclopentadienylzirconium trichloride, bis(cyclopentadienyl)zirconium diphenyl,bis(cyclopentadienyl)zirconium dimethyl, the alkyl substitutedcyclopentadienes, such as bis(ethyl cyclopentadienyl)zirconium dimethyl,bis(β-phenylopropylcyclopentadienyl)zirconium dimethyl,bis(methylcyclopentadienyl)zirconium dimethyl, and dihalide complexes ofthe above; di-alkyl, tri-alkyl, tetra-alkyl, and penta-alkylcyclopentadienes, such as bis(pentamethylcyclopentadienyl)zirconiumdimethyl, bis (1,2-dimethylcycloentadienyl)zirconium dimethyl,bis(1,3-diethylcyclopentadienyl)zirconium dimethyl and dihalidecomplexes of the above; silicone, phosphorous, and carbon bridgedcyclopentadiene complexes such as dimethylsilyldicyclopentadienylzirconium dimethyl or dihalide, methylphosphine dicyclopentadienylzirconium dimethyl or dihalide,and methylene dicyclopentadienylzirconium dimethyl or dihalide, carbenes represented by the formulae Cp₂Zr═CH₂ P(C₆ H₅)₂ CH₃, and derivatives of these compounds such as##STR2##

Bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)hafniumdimethyl, bis(cyclopentadienyl)vanadium dichloride and the like areillustrative of other metallocenes.

The ratio of aluminum in the alumoxane to total metal in themetallocenes can be in the range of about 0.5:1 to about 10,000:1, andpreferably about 5:1 about 1000:1.

The solvents used in the preparation of the catalyst system are inerthydrocarbons, in particular a hydrocarbon that is inert with respect tothe catalyst system. Such solvents are well known and include, forexample, isobutane, butane, pentane, hexane, heptane, octane,cyclohexane, methylcyclohexane, toluene, xylene and the like,

As a further control and refinement of polymer molecular weight, one canvary the concentration alumoxane. Higher concentrates of alumoxane inthe catalyst system results in higher polymer product molecular weight.

Since, in accordance with this invention, one can produce high viscositypolymer product at relatively high temperature, temperature does notconstitute a limiting parameter as with the prior artmetallocene/alumoxane catalyst. The catalyst systems described herein,therefore, are suitable for the polymerization of olefins in solution,slurry or gas phase polymerizations and over a wide range oftemperatures and pressures. For example, such temperatures may be in therange of about -60° C. to about 280° C. and especially in the range ofabout 50° C. to about 160° C. The pressures employed in the process ofthe present invention are those well known for, for example, in therange of about 1 to about 500 atmospheres and greater.

In a solution phase polymerization the alumoxane is preferably dissolvedin a suitable solvent, typically in inert hydrocarbon solvent such astoluene, xylene, and the like in molar ratios of about 5×10⁻³ M. Howevergreater or lesser amounts can be used.

The soluble metalleocenes can be converted to supported heterogeneouscatalyst by depositing said metallocenes on typical catalyst supportssuch as, for example, silica, alumina, and polyethylene. The solidcatalysts in combination with an alumoxane can be usefully employed inslurry and gas phase olefin polymerizations.

After polymerization and deactivation of the catalyst, the productpolymer can be recovered by processes well known in the art for removalof deactivated catalysts and solution. The solvents may be flashed offfrom the polymer solution and the polymer obtained extruded into waterand cut into pellets or other suitable comminuted shapes. Pigments,antioxidants and other additives, as is known in the art, may be addedto the polymer.

The polymer product obtained in accordance with this invention will havea weight average molecular weight in the range of about 1,400,000 toabout 500 and preferably 500,000 to about 1000.

The polydispersities (molecular weight distribution expressed as Mw/Mnare typically from 1.5 to 4.0. The polymers contain 1.0 chain endinsaturation per molecule. Broadened MW can be obtained by employing twoor more of the metal cyclopentadienyls in combination with the alumoxaneas described in cofiled application entitiled Process and Catalyst forProducing Polyethylene having a Broad Molecular Weight Distribution.

The polymers produced by the process of this present invention arecapable of being fabricated into a wide variety of articles, as is knownfor homopolymers of ethylene and copolymers of ethylene and higheralpha-olefins. The present invention is illustrated by the followingexamples.

EXAMPLES

In the examples following the molecular weights were determined on aWater's Associates Model No. 150C GPC (Gel Permeation Chromatography).The measurements were made by dissolving polymer samples in hottrichlorobenzene (TCB) and filtered. The GPC runs were performed at 145°C. in TCB at 1.5 ml/min using two Shodex A80 M/S Gel columns of 9.4 mminternal diameter from Perkin Elmer I.c. 300 milliter of 3.1 percentsolutions in TCB were injected and the chromotagraphic runs monitored atsensitivity equal -64 and scale factor equal 65. The samples were run induplicate. The integration parameters were obtained with a Water'sAssociates data module. A. antioxidant, N-phenyl-2-naphthylamine, wasadded to all samples.

In the examples following the alumoxane was prepared in the followingmanner:

600 cc of a 14.5% solution of triamethylaluminum (TMA) in heptane wasadded in 30 cc increments at 5 minute intervals, with rapid stirring, to200 cc toluene in a Zipperclave reactor under nitrogen and maintained at100° C. Each increment was immediately followed by the addition of 0.3cc water. The reactor was vented of methane after each addition. Uponcompletion of the addition, the reactor was stirred for 6 hours whilemaintaining the temperature at 100° C. The mixture, containing solublealumoxane and a small quanity of insoluble alumina, is allowed to coolto room temperature and settle. The clear solution containing thesoluble alumoxane is separated by decontation from the solids.

The molecular weights were determined by gel permeation chromatographyat 145° C. on a Waters GPC 150° C.

Example 1

A 1-liter stainless steel pressure vessel, equipped with an inclineblade stirrer, an external water jacket for temperature control, aseptum inlet and vent line, and a regulated supply of dry ethylene andnitrogen, was dried and deoxygenated with a nitrogen flow. 500 cc ofdry, degassed toluene was introduced directly into the pressure vessel.10.0 cc of 0.785 molar (in total aluminum) alumoxane was injected intothe vessel by a gas tight syringe through the septum inlet and themixture was stirred at 1,200 rpms and 80° C. for 5 minutes at 0 psig ofnitrogen. 0.091 mg bis(cyclopentadienyl) zirconium dichloride dissolvedin 2.0 ml of dry, distilled toluene was injected through the septuminlet into the vessel. After 1 minute, ethylene at 60 psig was admittedand while the reaction vessel was maintained at 80° C. The ethylene waspassed into the vessel for 30 minutes at which time the reaction wasstopped by rapidly venting and cooling. 13.6 gms of powdery whitepolyethylene having a Mn of 39,500 and a Mw of 140,000 with a molecularweight distribution of 3.5.

Example 2

A 1-liter stainless steel pressure vessel, equipped with an inclineblade stirrer, an external water jacket for temperature control, aseptum inlet and vent line, and a regulated supply of dry ethylene andnitrogen, was dried and deoxygenated with a nitrogen flow. 400 cc ofdry, degassed toluene was introduced directly into the pressure vessel.20.0 cc of alumoxane (0.785 mmoles in total aluminum) was injected intothe vessel by a gas tight syringe through the septum inlet and themixture was stirred at 1,200 rpms and 80° C. for 5 minutes at 0 psig ofnitrogen. 0.2101 mg bis(methylcyclopentadienyl) zirconium dichloridedissolved in 2.0 ml of dry, distilled toluene was injected through theseptum inlet into the vessel to give an Al/Zr ratio of 24×10³. After 1minute, ethylene at 60 psig was admitted for 30 minutes whilemaintaining the reaction vessel at 80° C. The reaction was stopped byrapidly venting and cooling. 28.6 gms of powdery white polyethylenehaving a Mn of 55,900 and a Mw of 212,000 with a molecular weightdistribution of 3.8 and activity (Kg/gM.hr.atm) of 467.

Example 3-6

Examples 3-6 were performed as Example 2 except that the metalloceneslisted in Table 1 were substituted for the metallocene in Example 2. Theresults of the examples are summarized in Table I.

Examples 7-9

Examples 7-9 were performed as Example 2 except that 0.2 mg ofmetallocenes as listed in Table 2 and 9.0 cc alumoxane were employedgiving an Al/Zr of 8×10³. The results are summarized in Table 2.

                  TABLE I                                                         ______________________________________                                        Substituted Cyclopentadiene (Cp) Ligand Effects                                                                       Activity                              Ex-                                     Kg/gM ·                      ample Catalyst.sup.a.                                                                             Mw      Mn    MWD   hr · atm                     ______________________________________                                        2     Cp.sub.2 ZrCl.sub.2                                                                         140,000 39,500                                                                              3.5   252                                   3     (MeCp).sub.2 ZrCl.sub.2                                                                     212,000 55,900                                                                              3.8   467                                   4     (EtCp).sub.2 ZrCl.sub.2                                                                     171,000 44,700                                                                              3.8   306                                   5     (B--PP--Cp).sub.2 ZrCl.sub.2                                                                282,000 78,200                                                                              3.6   335                                   6     (Me.sub.5 Cp).sub.2 ZrCl.sub.2                                                               63,000 13,200                                                                              4.7    71                                   ______________________________________                                         .sup.a. Al/Zr = 24,000                                                   

                  TABLE II                                                        ______________________________________                                                                               Activity                                                                      Kg/gM ·                       Example                                                                              Catalyst.sup.a.                                                                           Mw      Mn    MWD   hr · atm                      ______________________________________                                        7      (Me.sub.5 Cp).sub.2 ZrCl.sub.2                                                             47,300 13,200                                                                              3.6   142                                    8      (MeCp).sub.2 ZrCl.sub.2                                                                   180,000 48,300                                                                              3.7   278                                    9      (EtCp).sub.2 ZrCl.sub.2                                                                   184,000 50,000                                                                              3.7   281                                    ______________________________________                                         .sup.a. Al/Zr = 8,000                                                    

The physical properties of a polyethylene are largely determined by thepolymer molecular weight and the polymer density. The previous exampleshave demonstrated that through the ligand effect, one can control themolecular weight of polyethylenes. The following examples demonstratethat through the same ligand effects, one can control the polymerdensity in copolymerse such as ethylene copolymers. In addition, thecontrol of polymer density in the following examples is demonstrated atfixed reaction conditions indicating that density control is mediated byligand effects on the catalyst reactivity ratios.

Example 10

A 1-liter stainless steel pressure vessel, equipped with an inclineblade stirrer, an external water jacket for temperature control, aseptum inlet and vent line, and a regulated supply of dry ethylene andnitrogen, was dried and deoxygenated with a nitrogen flow. 400 cc ofdry, degassed toluene was introduced directly into the pressure vessel.10.0 cc of alumoxane solution (0.8 moles in total aluminum) was injectedinto the vessel by a gas tight syringe through the septum inlet and themixture was stirred at 1,200 rpms and 50° C. for 5 minutes at 0 psig ofnitrogen. 200 cc of liquid propylene at 25° C. was added resulting in apressure of 126.2 psig. 0.113 mg of bis(cyclopentadienyl)zirconiumdimethyl in 10 ml of toluene was injected through the septum inlet intothe vessel. Ethylene at 152.1 psig was admitted and the reaction vesselwas maintained at 50° C. The ethylene was passed into the vessel for 30minutes at which time the reaction was stopped by rapidly venting andcooling the reactor. 66.0 gms of copolymer having an intrinsic viscosityof 0.74 was isolated which contained 31 mole % propylene. The densitywas 0.854 g/cc at 23° C.

Example 11

A 1-liter stainless steel pressure vessel, equipped with an inclineblade stirrer, an external water jacket for temperature control, aseptum inlet and vent line, and a regulated supply of dry ethylene andnitrogen, was dried and deoxygenated with a nitrogen flow. 400 cc ofdry, degassed toluene was introduced directly into the pressure vessel.10.0 cc of alumoxane solution (0.8 moles in total aluminum) was injectedinto the vessel by a gas tight syringe through the septum inlet and themixture was stirred at 1,200 rpms and 50° C. for 5 minutes at 0 psig ofnitrogen. 200 cc of liquid propylene at 25° C. was then added resultingin a pressure of 126.2 psig. 0.102 mg of dimethylsilyl-cyclopentadienylzirconium chloride in 10 ml of toluene was injected through the septuminlet into the vessel. Ethylene at 152.4 psig was admitted and thereaction vessel was maintained at 50° C. The ethylene was passed intothe vessel for 30 minutes at which time the reaction was stopped byrapidly venting and cooling the reactor. 12.0 gms of copolymer having anintrinsic viscosity of 0.52 was isolated which contained 43 mole %propylene. The density was 0.854 g/cc at 23° C.

Example 12

A 1-liter stainless steel pressure vessel, equipped with an inclineblade stirrer, an external water jacket for temperature control, aseptum inlet and vent line, and a regulated supply of dry ethylene andnitrogen, was dried and deoxygenated with a nitrogen flow. 400 cc ofdry, degassed toluene was introduced directly into the pressure vessel.10.0 cc of alumoxane solution (0.8 moles in total aluminum) was injectedinto the vessel by a gas tight syringe through the septum inlet and themixture was stirred at 1,200 rpms and 50° C. for 5 minutes at 0 psig ofnitrogen. 200 cc of liquid propylene at 25° C. was then added resultingin a pressure of 126.2 psig. 0.417 mg ofbis(pentamethylcyclopentadienyl)zirconium dimethyl in 10 ml of toluenewas injected through the septum inlet into the vessel. Ethylene at 151.5psig was admitted and the reaction vessel was maintained at 50° C. Theethylene was passed into the vessel for 25 minutes at which time thereaction was stopped by rapidly venting and cooling the reactor. 30.5gms of copolymer having an intrinsic viscosity of 0.81 was isolatedwhich contained 3.6 mole % propylene. The density was 0.934 g/cc at 23°C.

The invention claimed is:
 1. A catalyst component for olefinpolymerization represented by one of the formulas:

    (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MeQ.sub.3-p

and

    R.sup.m.sub.s (C.sub.5 R'.sub.m).sub.2 MeQ'

wherein Me is Zr or Hf, (C₅ R'_(m)) is a cyclopentadienyl or substitutedcyclopentadienyl, each R', which can be the same or different, ishydrogen, an alkyl, alkenyl, aryl, alkylaryl, or arylalkyl radicalhaving from 1 to 20 carbon atoms or two adjacent carbon atoms are joinedtogether to form a C₄ -C₆ ring, R" is a dialkyl germanium or silicon, oran alkyl phosphine or amine radical bridging two (C₅ -R'_(m)) rings,each Q which can be the same or different is aryl, alkyl, alkenyl,alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms orhalogen, Q' is an alkylidene radical having from 1 to 20 carbon atoms, sis 1, p is 1, m is 4; and at least one R' is a hydrocarbyl radical whenat least one Q is an alkyl radical or halogen.
 2. A compound representedby one of the formulas:

    (C.sub.5 R'.sub.4)R"(C.sub.5 R'.sub.4)MeQ.sub.2

and

    R"(C.sub.5 R'.sub.4).sub.2 MeQ'

wherein Me is Zr or Hf, (C₅ R'₄) is a substituted cyclopentadienyl, eachR', which can be the same or different, is selected from hydrogen, analkyl, alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20carbon atoms or two adjacent carbon atoms are joined together to form aC₄ -C₆ ring, at least one R' is other than hydrogen on at least one (C₅R'₄), R" is a germanium, silicon, phosphine or amine radicalsubstituting on and bridging two (C₅ R'₄) rings, each Q which can be thesame or different is an aryl, alkyl, alkenyl, alkylaryl, or arylalkylradical having from 1 to 20 carbon atoms or halogen, and Q' is analkylidene radical having from 1-20 carbon atoms.
 3. The compound ofclaim 2 wherein at least one (C₅ R₄) group is a dialkyl, a tri-alkyl, ora tetraalkyl substituted cyclopentadienyl moiety.
 4. The compound ofclaim 2 wherein only one (C₅ R'₄) includes at least one R' that is ahydrocarbon radical.
 5. A compound represented by one of the formulas:

    (C.sub.5 R'.sub.4)R"(C.sub.5 R'.sub.4)MeQ.sub.2

and

    R"(C.sub.5 R'.sub.4).sub.2 MeQ'

wherein Me is Zr or Hf, (C₅ R'₄) is a substituted cyclopentadienyl, eachR', which can be the same or different, is selected from hydrogen, analkyl, alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20carbon atoms or two adjacent carbon atoms are joined together to form aC₄ -C₆ ring, at least one R' is other than hydrogen on at least one (C₅R'₄), R" is a phosphine or amine radical substituting on and bridgingtwo (C₅ R'₄) rings, each Q, which can be the same or different is anaryl, alkyl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to20 carbon atoms or halogen, and Q' is an alkylidene radical having from1-20 carbon atoms.
 6. A compound represented by one of the formulas:

    C.sub.5 R'.sub.4)R"(C.sub.5 R'.sub.4)MeQ.sub.2

and

    R"(C.sub.5 R'.sub.4).sub.2 MeQ'

wherein Me is a Zr, (C₅ R'₄) is a substituted cyclopentadienyl, each R',which can be the same or different, is hydrogen, an alkyl, alkenyl,aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbon atoms ortwo adjacent carbon atoms are joined together to form a C₄ -C₆ ring, atleast one R' is other than hydrogen on at least one (C₅ R'₄), R" is agermanium, phosphine or amine radical substituting on and bridging two(C₅ R'₄) rings, each Q which can be the same or different is an aryl,alkyl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20carbon atoms or halogen, and Q' is an alkylidene radical having from1-20 carbon atoms.
 7. A compound represented by one of the formulas:

    (C.sub.5 R'.sub.4)R"(C.sub.5 R'.sub.4)MeQ.sub.2

and

    R"(C.sub.5 R'.sub.4).sub.2 MeQ'

wherein Me is Hf, (C₅ R'₄) is a substituted cyclopentadienyl, each R',which can be the same or different, is selected from hydrogen, an alkyl,alkenyl, aryl, alkylaryl or arylalkyl radical having from 1 to 20 carbonatoms or two adjacent carbon atoms are joined together to form a C₄ -C₆ring, at least one R' is other than hydrogen on at least one (C₅ R'₄),R" is a C₁ -C₄ alkylene radical, a germanium, silicon, phosphine oramine radical substituting on and bridging two (C₅ R'₄) rings, each Qwhich can be the same or different is an aryl, alkyl, alkenyl,alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms orhalogen, and Q' is an alkylidene radical having from 1-20 carbon atoms.8. A compound represented by one of the formulas:

    (C.sub.5 R'.sub.4)R"(C.sub.5 R'.sub.4)MeQ.sub.2

and

    R"(C.sub.5 R'.sub.4).sub.2 MeQ'

wherein Me is Group Zr or Hf, (C₅ R'₄) is a substitutedcyclopentadienyl, each R', which can be the same or different, isselected from hydrogen, an alkyl, alkenyl, aryl, alkylaryl or arylalkylradical having from 1 to 20 carbon atoms or two adjacent carbon atomsare joined together to form a C₄ -C₆ ring, at least one R' is other thanhydrogen on at least one (C₅ R'₄), R" is a C₁ -C₄ alkylene radical, agermanium, silicon, phosphine or amine radical substituting on andbridging two (C₅ R'₄) rings, each Q which can be the same or differentis an aryl, alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20carbon atoms, and Q' is an alkylidene radical having from 1-20 carbonatoms.